200530248 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種製備式I之無金屬酞菁之方法200530248 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for preparing a metal-free phthalocyanine of formula I
其係在氨存在下於具有沸點為至少12〇艺（在標準壓力下）之 惰性溶劑内轉化式la之鄰位酞二腈，It is the conversion of o-phthalophthalonitrile of formula la in an inert solvent having a boiling point of at least 120 ° C (under standard pressure) in the presence of ammonia,
其中，在式I或la中，變數n可採用丨，2,3或4之值而R基表示5 或6員飽和含氮雜環，視需要經一或二個烷基取代， 其係藉由環氮原子鍵合至苯環且其仍可包含一或二個附加 氮原子或附加氧或硫原子， 其包括在驗金屬氫氧化物或驗金屬碳酸鹽存在下實施轉 化。 【先前技術】 無金屬酞菁之製備通常在高沸 自異假啕哚二亞胺， 通吊在鬲沸點溶劑内實施，該溶劑來 例如，揭示於US 3,509，146，或在鹼如 98436.doc 200530248 氨存在下來自鄰位酞二腈或異假吲味二亞胺，例如揭示於 P· J. Brach，S. J. Grammatica，〇· a. Ossanna and L·Among them, in formula I or la, the variable n can take the values of 丨, 2, 3, or 4 and the R group represents a 5 or 6-membered saturated nitrogen-containing heterocyclic ring, and if necessary, is substituted by one or two alkyl groups, which is borrowed from Bonded by a ring nitrogen atom to a benzene ring and which may still contain one or two additional nitrogen atoms or additional oxygen or sulfur atoms, which includes conversion in the presence of a metal hydroxide or a metal carbonate. [Prior art] The preparation of metal-free phthalocyanine is usually carried out in a high-boiling autoiso-isopyridoxine diimide, which is carried out in a fluorene boiling point solvent, which is disclosed, for example, in US 3,509,146, or in a base such as 98436. doc 200530248 In the presence of ammonia, it is derived from ortho-phthalodinitrile or iso-pseudoindimine, as disclosed in, for example, P. J. Brach, SJ Grammatica, 〇 · a. Ossanna and L ·
Weinberger，J. Heterocyclic Chem·，7 (197〇)，i4〇3_14〇5 0 然而’使用上述文件所表示之製備方法之式I之無金屬酜 脊之製備導致令人無法滿意之產率。因此，例如，根據 P.J.BraCh等人之指示可自3-(3-甲基哌啶基）酞二腈獲得丨（4) 8(11)，15(18)，22(25)-四（3·甲基哌啶基）酞菁，其確實具有 高純度但僅具有37%之低產率。 【發明内容】 因此，本發明之目的為提供一種可製備具有高純度及高 產率之式I之無金屬醜菁之方法。此目的可由前述方法達 式1及1基為5或6員飽和含氮雜環，視需要經—或一 個W取代，其係藉由適當環氮原子鍵合至苯環且： 仍可包含-或二個附加氮原子或附加氧或硫原子。、 R基較佳為6員飽和含氮雜環’視需要經一或二個 烧基取代’其係藉由環氮原子鍵合至苯環且其仍-^ 個附加氮原子。 各一 該雜環之例為吡咯啶·丨_其 -甲美…… 或甲基响终1·基、24- :曱,3·乙基㈣“基，唆·，: 基吡唑啶-1-基、咪唑啶·κ 及5-甲 Α 土 ’ 或5-甲基口米口坐口定 基、3唑啶-3-基、2-，4-或5_甲其广^ 定一1· 盆, 甲基亏唑啶基、異啰唑啶9 基、3-，（或5-甲基異口咢唑啶定·2、 基、喊啶小基、（CVC4n、 哌啶-1-基，例如，2-，3-，4_甲美式 凡土） 土或乙基哌啶基、2,6_二 98436.doc 200530248 基味咬-1-基、來"1井-1-基、院基）喊啡-1-基，例如， 4-曱基-或4-乙基喊命-1 -基、嗎4 -4-基、硫代嗎p林—4-基或 S，S -二氧化硫代嗎p林-4 -基。 R特佳為經一或二個C1-CU-烧基取代之旅σ定-1 _基或味口井 -1-基。 作為雜環之可能取代基之（^-(^或C^C4·烷基之例為甲 基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第 三丁基、戊基、異戊基、辛戊基、第三戊基、己基、2_甲 基戊基、庚基、庚-3-基、辛基、2-乙基己基及異辛基。 根據本發明方法之原理可使用式Ia之不同化合物之混合 物，在各情況下，在η值及/或其R基之化學性質及/或其相 對位置對敝二腈之腈基方面其互相不同。 然而，式la之化合物較佳為純化合物，其具有指定變數打 之值’對η較佳相同之r基等於2,3或4。 特佳的是’在式1或la中，變數η採用值1。 在此方面，亦可述及，不僅對於化學上不同r基而且在相 同R基之最後較佳情況下，所得幻之化合物可由定位異構 物之混合物組成。此係由以下實例（參照，·Β)正丁二醇之轉 化Ί舉例說明。 $悉此技藝者已知供製備無金屬酿菁之所有溶那 性溶劑’但其具有_為至少12Gt(在標準壓力下）。 根據本發明方、、七％ m 月方去所用之溶劑係選自乙二醇、二乙二 丙二醇、1，2-丁二醆、" " ，-丁 一醇、1，4_丁 二醇、2,3-丁二醇 上述二醇類之單盥- ”—（Li'C4_ 烷基）醚、2-[二（Cl_C4•烷基） 98436.doc 200530248 基]乙醇及3-[二（Ci-C4-烷基）胺基]丙醇。上述二醇類之單與 二（CVCV烷基）醚及2_[二（cvcv烷基）胺基]乙醇及％[二 (q-C4-烷基）胺基]丙醇之適當Ci_C4_烷基為甲基 '乙基、正 丙基、異丙基、正丁基、異丁基、第二丁基或第三丁基。 在單與二醚之情況下，烷基通常為曱基或正丁基，在胺基 酵之情況下，通常為甲基。最好使用上述二醇與[二 (Ci-CU-烧基）胺基]丙醇之單鱗。 此外，當自上述基選擇特定溶劑時，具有沸點為至少 °c之規定自然可看到。 特佳為提供正丁二醇及3_二甲基胺基丙醇。 較佳使用氫氧化納、氫氧化卸、碳酸納及碳酸卸，特佳 為氫氧化鈉及碳酸鉀之鹼金屬氫氧化物或鹼金屬碳酸鹽。 上述鹼之一通常根據本發明方法加入；然而，亦可^用 一種以上驗之混合物。 鹼或鹼混合物之比例，以式la之化合物之莫耳數計，通 常為0.5至1〇莫耳％，較佳為}至6莫耳％。 根據本發明之轉化通常在具有對應攪拌裝置及視需要改 良父互混合之内部配件如擋板之標準反應器内實施。 氨通常在怪定體積流速下導入在反應器底部之反應混合 物内。在此方面，每單元時間計量之氨量可使用傳統方法， 例如’藉收集於稀釋醋酸内及後續滴定校正。 氨量以式la之化合物之莫耳數計，較佳為至少二莫耳當 量，因為假定氨根據以下化學等式以催化方式作用·· 98436.doc 200530248Weinberger, J. Heterocyclic Chem., 7 (197〇), i403--1450. However, the preparation of the metal-free ridges of formula I using the preparation method indicated in the above document resulted in unsatisfactory yields. Therefore, for example, according to the instructions of PJBraCh et al., It can be obtained from 3- (3-methylpiperidinyl) phthalonitrile 丨 (4) 8 (11), 15 (18), 22 (25) -tetra (3 -Methylpiperidinyl) phthalocyanine, which does have a high purity but only a low yield of 37%. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for preparing a metal-free ugly cyanine of formula I with high purity and high yield. This purpose can be achieved by the aforementioned method of formula 1 and 1 is a 5 or 6-membered saturated nitrogen-containing heterocyclic ring, optionally substituted by-or a W, which is bonded to the benzene ring by an appropriate ring nitrogen atom and: may still include- Or two additional nitrogen atoms or additional oxygen or sulfur atoms. The R group is preferably a 6-membered saturated nitrogen-containing heterocyclic ring ', optionally substituted with one or two alkyl groups, which is bonded to a benzene ring through a ring nitrogen atom and which still has-^ additional nitrogen atoms. An example of each of these heterocycles is pyrrolidine · 丨 its-memetyl ... or a methyl ring-terminated 1-yl group, 24--, fluorene, 3 · ethyl fluorenyl group, hydrazine, -ylpyrazidine- 1-yl, imidazolidine κ and 5-methyl Α 'or 5-methyl acetaminophen, 3 oxazolyl-3-yl, 2-, 4-, or 5-methyl-2-methyl · Basin, methyl oxazolidinyl, isoxazolyl 9-yl, 3-, (or 5-methylisoxazolidinidine 2, 2, yl, pyridyl), (CVC4n, piperidin-1- Base, for example, 2-, 3-, 4_methyl American terrane) earth or ethyl piperidinyl, 2,6_ di 98436.doc 200530248 base taste bite-1-yl, come " 1 well-1- Base, or base), for example, phenanthrene-1-yl, for example, 4-fluorenyl- or 4-ethylsulfonyl-1 -yl, 4-4-yl, thiomorphin-4-yl, or S, S-thiomorpholine ply-4 -yl. R is particularly preferably substituted by one or two C1-CU-yl radicals sigma-1 -yl or Weikoujing -l -yl. Possibility as a heterocyclic ring Examples of (^-(^ or C ^ C4 · alkyl) are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, and pentyl , Isopentyl, octyl, third pentyl, hexyl, 2-methylpentyl, heptyl Base, hept-3-yl, octyl, 2-ethylhexyl and isooctyl. According to the principles of the method of the invention, mixtures of different compounds of the formula Ia can be used, in each case at the value η and / or R The chemical properties of the radicals and / or their relative positions are different from those of the nitrile radicals of acrylonitrile. However, the compound of formula la is preferably a pure compound which has a value designated by the variable 'r is preferably the same as r Equal to 2, 3 or 4. Particularly preferred is' in formula 1 or la, the variable η takes the value 1. In this respect, it can also be mentioned that it is better not only for chemically different r groups but also at the end of the same R group In this case, the obtained phantom compound can be composed of a mixture of ortho isomers. This is illustrated by the following example (reference, · B) for the conversion of n-butanediol. All of the soluble solvents' but have at least 12 Gt (under standard pressure). According to the present invention, the solvent used is 7% selected from ethylene glycol, diethylene glycol, 1, 2-butanediol, " ", -butanol, 1,4-butanediol, 2,3-butanediol Monodiols of the diols-"— (Li'C4_alkyl) ether, 2- [di (Cl_C4 • alkyl) 98436.doc 200530248 based] ethanol and 3- [di (Ci-C4-alkyl) amine Alkyl] propanol. The above diols are mono- and di (CVCV alkyl) ethers and 2- [di (cvcv alkyl) amino] ethanol and% [di (q-C4-alkyl) amino] propanol. Suitable Ci_C4-alkyl is methyl'ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, or third butyl. In the case of mono- and diethers, the alkyl group is usually fluorenyl or n-butyl, and in the case of amino fermentation, it is usually methyl. It is preferable to use a monoscale of the above-mentioned diol and [bis (Ci-CU-alkyl) amino] propanol. In addition, when a specific solvent is selected from the above-mentioned groups, a rule having a boiling point of at least ° c is naturally seen. Tejia provides n-butanediol and 3-dimethylaminopropanol. Sodium hydroxide, hydroxide hydroxide, sodium carbonate, and carbonate carbonate are preferably used. Particularly preferred are alkali metal hydroxides or alkali metal carbonates of sodium hydroxide and potassium carbonate. One of the above-mentioned bases is usually added according to the method of the present invention; however, more than one mixture may be used. The proportion of the base or base mixture, based on the mole number of the compound of formula la, is usually 0.5 to 10 mole%, preferably} to 6 mole%. The conversion according to the present invention is usually carried out in a standard reactor with corresponding agitation devices and internal fittings such as baffles that improve the mixing of the parent if necessary. Ammonia is usually introduced into the reaction mixture at the bottom of the reactor at an odd volume flow rate. In this regard, the amount of ammonia measured per unit time can be corrected using conventional methods, such as by 'collecting in diluted acetic acid and subsequent titration. The amount of ammonia is based on the molar number of the compound of formula la, preferably at least two molar equivalents, since it is assumed that ammonia acts catalytically according to the following chemical equation. 98436.doc 200530248
(R)〇 導入氨之時間通常為方干小時。在此方面，由申+青人在 實驗室規模上實施之試驗可作為資訊幫助。例如，在$ 〇 〇 毫升具有踏板式攪拌器之圓底燒瓶及在具有盤狀混合器金 擋板之2升反應器内，在全部導入時間為9小時（在加熱相期 間2小時及在最後溫度下7小時）後，可達成最低量二莫耳當 量氨，氣體之導入係使用浸泡管在燒瓶或反應器之底部實 施。 反應溫度通常為140與17(TC之間，對特定惰性溶劑之最 適合反應溫度可由熟悉此技藝者以簡單方式藉例行初步實 驗決定。例如，在申請人用溶劑3_二甲基胺基丙醇及正丁 二醇之實驗中，最高產率係分別在反應溫度為約15〇與 °C下測定。 式la之化合物（莫耳數）對惰性溶劑（體積）之比通常約二 莫耳至1升，然而，在各個情況下，其可在此值以上及此值 98436.doc 200530248 以下。 【貫施方式】 實例： 1(4)，8(11)，15(18)，22(25)-四（3-甲基哌啶基）酞菁之製備： A)3-二甲基胺基丙醇之轉化 225.3克（1.00莫耳）3_(3-甲基哌啶基）駄二腈在周圍溫度 下以攪拌方式（150轉數/分鐘）導入500毫升3_二甲基胺基$ 醇於2升法蘭燒瓶内。隨後加入4· 85克（〇·〇35莫耳；3 5莫耳 %)碳酸鉀。全部“.丨克⑺⑻莫耳）氨藉由具有體積流速為約 83毫升/分鐘之浸泡管以氣體形式導入反應混合物内歷9小 時（在加熱相期間2小時及在反應相期間7小時），反應混合物 加熱至最後溫度為150°C並保持在此溫度15小時。其後，黑 色反應溶液冷卻至50 °C而1000毫升甲醇在2小時内攪拌加 入其中，以完全沉殿冷卻時所產生之固體。懸浮液在5〇它 下攪拌另外一小時，然後冷卻至周圍溫度並在吸力過濾器 上過濾。濾餅首先用800毫生甲醇，然後用1〇〇〇毫升水洗 滌，最後拉住乾燥。 在60°C真空下乾燥後，可得產率為ι7〇·4克（以純物質計， 理論上70%)之黑色粉末。 自3-二曱基胺基丙醇再結晶3次及自正丁二醇再結晶i次 之樣品以分析方式實際上為純粹。元素分析產生： C56H62N12 計异值 C 74.47% Η 6.93% Ν 18.61% (903.2克/莫耳） 貫測值 C74.8% Η 6.9% Ν 18.2% Β)正丁二醇之轉化 98436.doc 200530248 使用正丁二醇代替3'二曱基胺基丙醇作為 化及16〇°C用作最後溫度（比較於根據A之實/性溶劑供轉 改變剩餘參數）並提供所欲產物 、驗較序具有未 根據A)作為具有以下結構之不：產率及純度’其(亦 在· 疋位異構物之混合物存(R). The time for introducing ammonia is usually dry hours. In this regard, the tests carried out by Shen + Qingren on a laboratory scale can serve as an information aid. For example, in a round bottom flask with a pedal stirrer and a 2-liter reactor with a disc-shaped mixer gold baffle, the total introduction time is 9 hours (2 hours during the heating phase and at the end After 7 hours at the temperature), a minimum amount of two molar equivalents of ammonia can be achieved. The introduction of the gas is carried out at the bottom of the flask or reactor using an immersion tube. The reaction temperature is usually between 140 and 17 ° C. The most suitable reaction temperature for a particular inert solvent can be determined by routine preliminary experiments in a simple manner by those skilled in the art. For example, the applicant uses a solvent of 3-dimethylamino group. In experiments with propanol and n-butanediol, the highest yields were determined at reaction temperatures of about 15 ° and ° C. The ratio of the compound (mole number) to the inert solvent (volume) of formula la is usually about two moles. Ear to 1 liter, however, in each case, it can be above this value and below this value 98436.doc 200530248. [Performance] Examples: 1 (4), 8 (11), 15 (18), 22 (25) Preparation of Tetrakis (3-methylpiperidinyl) phthalocyanine: A) Conversion of 3-dimethylaminopropanol: 225.3 g (1.00 mole) of 3- (3-methylpiperidinyl) fluorene Dinitrile was introduced into a 2-liter flange flask with 500 ml of 3-dimethylamino alcohol at agitated (150 rpm) at ambient temperature. Subsequently, 4.85 g (0.035 mol; 35 mol%) of potassium carbonate was added. All ". 丨 grams of mol) ammonia was introduced into the reaction mixture as a gas through an immersion tube with a volume flow rate of about 83 ml / min for 9 hours (2 hours during the heating phase and 7 hours during the reaction phase), The reaction mixture was heated to a final temperature of 150 ° C and kept at this temperature for 15 hours. Thereafter, the black reaction solution was cooled to 50 ° C and 1000 ml of methanol was added thereto with stirring within 2 hours, so as to completely produce when the temple was cooled down. Solid. The suspension was stirred at 50 ° C for another hour, then cooled to ambient temperature and filtered on a suction filter. The filter cake was first washed with 800 milliliters of methanol, then 1000 milliliters of water, and finally pulled to dryness After drying under vacuum at 60 ° C, a black powder with a yield of 70.4 g (based on pure substance, theoretically 70%) can be obtained. Recrystallize 3 times from 3-difluorenylaminopropanol and from The n-butanediol recrystallized sample is actually pure by analysis. Elemental analysis yields: C56H62N12 Calculated different value C 74.47% Η 6.93% Ν 18.61% (903.2 g / mole) Continuous measured value C74.8% Η 6.9% Ν 18.2% Β) Conversion of n-butanediol 98436.doc 200530248 Use n-butanediol instead of 3 'difluorenylaminopropanol as the final chemical and 16 ° C as the final temperature (compared to the remaining parameters based on the actual solvent of A) and provide the desired The product has no basis according to A) as having the following structure: Yield and purity 'its (also a mixture of
98436.doc -12-98436.doc -12-